Manson, Jamie L. and Manson, Zachary E. and Sargent, Ashley and Villa, Danielle Y. and Etten, Nicole L. and Blackmore, William J.A. and Curley, Samuel P.M. and Williams, Robert C. and Brambleby, Jamie and Goddard, Paul A. and Ozarowski, Andrew and Wilson, Murray N. and Huddart, Benjamin M. and Lancaster, Tom and Johnson, Roger D. and Blundell, Stephen J. and Bendix, Jesper and Wheeler, Kraig A. and Lapidus, Saul H. and Xiao, Fan and Birnbaum, Serena and Singleton, John (2020) 'Enhancing easy-plane anisotropy in bespoke Ni(II) quantum magnets.', Polyhedron., 180 . p. 114379.
Abstract
We examine the crystal structures and magnetic properties of several S = 1 Ni(II) coordination compounds, molecules and polymers, that include the bridging ligands HF2-, AF62- (A = Ti, Zr) and pyrazine or non-bridging ligands F-, SiF62-, glycine, H2O, 1-vinylimidazole, 4-methylpyrazole and 3-hydroxypyridine. Pseudo-octahedral NiN4F2, NiN4O2 or NiN4OF cores consist of equatorial Ni-N bonds that are equal to or slightly longer than the axial Ni-Lax bonds. By design, the zero-field splitting (D) is large in these systems and, in the presence of substantial exchange interactions (J), can be difficult to discriminate from magnetometry measurements on powder samples. Thus, we relied on pulsed-field magnetization in those cases and employed electron-spin resonance (ESR) to confirm D when J << D. The anisotropy of each compound was found to be easy-plane (D > 0) and range from ≈ 8-25 K. This work reveals a linear correlation between the ratio d(Ni-Lax)/d(Ni-Neq) and D although the ligand spectrochemical properties may also be important. We assert that this relationship allows us to predict the type of magnetocrystalline anisotropy in tailored Ni(II) quantum magnets.
Item Type: | Article |
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Full text: | Publisher-imposed embargo (AM) Accepted Manuscript File format - PDF (2993Kb) |
Full text: | (VoR) Version of Record Available under License - Creative Commons Attribution Non-commercial No Derivatives. Download PDF (5560Kb) |
Status: | Peer-reviewed |
Publisher Web site: | https://doi.org/10.1016/j.poly.2020.114379 |
Publisher statement: | © 2020 The Authors. Published by Elsevier Ltd. This an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). |
Date accepted: | 17 January 2020 |
Date deposited: | 24 January 2020 |
Date of first online publication: | 22 January 2020 |
Date first made open access: | No date available |
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